Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0026—Low foaming or foam regulating compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3753—Polyvinylalcohol; Ethers or esters thereof

Definitions

• washing apparatus has been directed toward further increasing the intensity of the liquor motion as well as the water volume cycled per minute, and in this way to further improve the mechanical cleansing effect.
• conventional washing agents such as higher molecular weight sulfates or sulfonates, caused too much foam.
• nonionic surface-active agents such as ethylene oxide addition products to alkylphenols or polypropylene glycols, have been preferred. These products, as well, were found to have a relatively high foaming tendency in the ranges of concentration required for satisfactory wetting and cleansing effect when used in the modern dishwashing machines.
• An object of the invention is the obtention of highly effective and extremely low-foaming dish and general purpose detergent combinations for dishwashers which do not cause any waste water problems due to their biological harmiessness.
• a further object is the obtention of low-foaming rinsing and washing compositions adapted for dishwashers consisting essentially of (A) from 70 percent to 98 percent by weight of water-soluble polyvinyl alcohols having a molecular weight of between 1,000 and 4,000, and (B) from 2 percent to 30 percent by weight of interface active compounds based on aikyiene oxide adducts selected from the group consisting of l) a polyoxypropyiene glycol having an average number of xypropylene units of between l7 and 86, adducted with from 0 to 30 mol percent of oxyethylene units, the total number of oxypropylene and oxyethylene units in said adduct being 100 mol percent (2) a propylene oxide adduct of a hydrocarbon compound having from two to 10 carbon atoms and at least two reactive hydrogen atoms selected from the group consisting of aiitanes, benzene and aikylbenzenes, substituted with substituent
• R represents a radical having from eight to 36 carbon atoms selected from the group consisting of alkyi, alkenyl, alkadienyl, monohydroxyalkenyl and alkylphenyl and Y represents a bridging link selected from the group consisting of 0, S, COO, NH, CON", and S0,Nl-l; adducted first with ybutylene, said oxycthylene being from 0 to 70 mol percent of the total amount of oxyalkylene units present; from 2 to oxypropylene and oxybutylene units being present in said adduct.
• Another object of the invention is the obtention of aqueous solutions of the above low-foaming rinsing and washing compositions.
• a yet further object of the invention is the development of a method of washing and rinsing solid articles which comprises forcefully contacting said solid articles with water containing from 0.01 to 0.5 grams per liter of the above low-foaming rinsing and washing compositions.
• the present invention relates to low-foaming rinsing and washing compositions adapted for dishwashers based on polyvinylalcohol and nonionic foam-suppressing agents, which is distinguished by a good compatibility with waste waters and harmlessness against fish and other water organisms.
• compositions are characterized by a content of (A) from 70 percent to 98 percent by weight of water-soluble poiyvinylalcohois having a molecular weight of between 1,000 and 4,000, and (B) from 2 percent to 30 percent by weight of interface active compounds with a content of from 2 to 90 oxyalkylene units selected from the group consisting of oxypropylene and oxybutylene and preferably a further content of l or more oxycthylene units where the amount of oxypropylene and oxybutylene units is at least 30 percent of the total amount of oxyalkylene units.
• the claimed combination is extraordinarily low foaming even under extreme application conditions, both in household dishwashers as well as in commercial dishwashers.
• the compositions of the invention possess an excellent wetting effect with respect to hard surfaces such as porcelain, synthetics or metals.
• the combinations of the invention are particularly suitable as lowfoaming, clear, rinsing agents for dishes and silverware of all kinds, possibly with a preceding alkaline prewashing phase, as well as for washing and clear rinsing of drinking glasses and other glassware.
• the special advantage of the combinations of the invention with respect to known low-foaming rinsing agents is that the requirement for nontoxicity with respect to fish and other water organisms is met to a satisfactory degree.
• poiyvinylalcohol used as the component A is only slightly biologically decomposed, it can yet be considered as physiologically harmless since it does not exhibit any toxic properties, whatsoever, toward those organisms which live in water.
• the interface active compounds of type B are biologically decomposed to a satisfactory degree, particularly where they have straight alltyi radicals and a relatively short polyoxyalkylene chain.
• the water-soluble polyvinylalcohols having a molecular weight of between l,000 and 4,000 used as component A are known products and are used in the trade. They can be obtained, for instance, by means of hydrolysis of polyvinyl acetates of the corresponding degree of polymerization. Within the framework of this invention such water-soiuble polyvinylalcohols are preferred which have a hydrolysis degree of 85 percent to 90 percent and have molecular weights of approximately 1,000 to 3,000.
• propylene oxide polymers come into consideration such as are obtained by means of polymerization of propylene oxide or addition of propylene oxide to lower molecular weight aliphatic compounds containing at least two reactive hydrogen atoms, particularly hydroxyl or amino groups with approximately two to six carbon atoms or to corresponding compounds with six to l carbon atoms.
• the reaction is carried out according to known methods in the presence of alkaline catalysts, preferably under pressure.
• the corresponding propylene oxide polymers have molecular weights of 1,000 to 5,000 or from 17 to 86 oxypropylene units, preferably 1,700 to 4,!00.
• Preferably up to 30 mol percent of ethylene oxide is added as calculated on the basis of the total amount of alkylene oxides.
• the propylene oxide polymers of the above type are preferably either polyoxypropylene glycols having an average number of oxypropylene units of between 17 and 86, corresponding to molecular weights of 1,000 to 5,000, and more particularly polyoxypropylene glycols having an average number of oxypropylene units of between 29 and 70, corresponding to molecular weights of [,700 to 4,100, adducted with from 0 to 30 mol percent of oxyethylene units, the total number of oxypropylene and oxyethyiene units in said polymer being I00 moi percent; as well as propylene oxide adducts of hydrocarbon compounds having from two to carbon atoms and at least two reactive hydrogen atoms, preferably selected from the group consisting of alkanes, benzene and aikylbenzenes, substituted with substituents selected from the group consisting of hydroxy, amino, and mixtures thereof, said propylene oxide adduct having an average number of oxypropylene units of between and
• the propylene oxide polymers of type B are obtained in a known way by polymerization of propylene oxide to obtain poiyoxypropylene glycols or by the addition of propylene oxide to compounds having from two to 10 carbon atoms and at least two reactive hydrogen atoms.
• the polymerization and adduct formation is conducted in the presence of alkaline catalysts such as sodium hydroxide, sodium methylate and others.
• the compounds having from two to 10 carbon atoms which are adducted are aliphatic compounds having two to six carbon atoms such as ethylene glycol, propylene glycol, 1,6- hexanediol glycerine, sugar alcohols, ethylene diamine, alkanolamines, for example, ethanolamine, dipropanolamine, etc., as well as aromatic and aliphatic aromatic compounds having six to 10 carbon atoms, such as phenyiene diamine, pethanolaniline, etc., adduct of 4.5 mois of ethylene oxide to polypropylene glycol with a molecular weight of 1,750; the adduct of 7 or 16 mois of ethylene oxide to a polypropylene glycol with a molecular weight of 2,750; the adduct of 8.5 mois of ethylene oxide to a polypropylene glycol consisting of 56 oxypropylene radicals; the adduct of 35 mols of propylene oxide to glycerine; the
• Another method for the preparation of suitable compounds of type B consists in the addition of 2 to 90 mois of propylene oxide and/or butylene oxide to higher molecular weight compounds with eight to 36 carbon atoms which contain reactive hydrogen atoms bonded through the heteroatoms 0, S and N.
• the higher molecular weight compounds may be aliphatic, aliphatic-cycloaliphatic or aliphatic-aromatic.
• the aliphatic compounds possess higher molecular weight radicals with eight to 36, and preferably 10 to 20 carbon atoms and are preferably of the formula:
• R-Yl-l wherein R represents a radical having from eight to 36 carbon atoms selected from the group consisting of alkyl, alkenyl, alkadlenyl and hydroxy-aikenyl, H represents a replaceable hydrogen and Y represents a bridging link selected from the group consisting of:
• the aliphatic-aromatic compounds possess higher molecular weight radicals with 12 to 22, and preferably i4 to l8 carbon atoms and are preferably of the formula:
• R'-Y-ll wherein Y and H have the above-assigned values and R represents a radical having 12 to 22 carbon atoms selected from the group consisting of alkylphenyl, alkylnaphthyl, al
• hydrocarbon radicals R and R may contain conventional substituents such as hydroxyl groups, halide atoms, or alkyl side chains.
• aliphatic, aliphatic-cycloaliphatic or aliphatic-aromatic compounds such as alcohols, alltylphenols, carboxylic acids, mercaptans, amines, carboxylic acid amides or alkanolamides, sulfonic acid amides, and the like with eight to 36, preferably 12 to 18 carbon atoms.
• the alkyl radicals can carry substitutes such as halogen atoms or can have side chains.
• adducts are used which, in addition to oxypropylene and/or oxybutylene units, have ,oxyethylene units as well.
• the number of oxypropylene and/or oxybutyiene units should be at least 30 percent by moi of the total oxyalkylene units.
• the alkylene oxide units to be added consist of 70 mol percent or less of ethylene oxide and at least 30 to mol percent of propylene oxide and/or butylene oxide.
• ethylene oxide is added in the first step and thereafter propylene oxide and/or butylene oxide is then added.
• the reaction is accomplished in the usual manner, for example, by utilizing pressure in the presence of alkaline catalysts.
• Compounds of type B may also be prepared by reacting higher molecular weight aliphatic or aliphatic-aromatic compounds with compounds containing prepared polyoxyalkylene chains, for example, the esterification of higher molecular weight carboxylic acids with polypropylene glycols or the etherification of higher molecular weight alcohols with polypropylene glycols.
• Examples for suitable compounds of group B are the follow ing: the adduct of 2 mois of propylene oxide to dodecyl alcohol; the adduct of 3 mois of propylene oxide to a fatty alcohol mixture of the chain length C to C the adduct of 3 mois of ethylene oxide and 3 mois of propylene oxide to dodecyl alcohol; the adduct of 2 mois of ethylene oxide and 4 mois of propylene oxide or of 3 mois of ethylene oxide and 3 mois of propylene oxide to a fatty alcohol mixture of the chain length C to C the adduct of 7 mois of ethylene oxide and i0 mois of propylene oxide or of 9 mois of ethylene oxide and 16 mois of propylene oxide to a fatty alcohol mixture of the chain length C to C the adduct of 10 mois of ethylene oxide and 20 mois of propylene oxide to a fatty alcohol mixture of the chain length C to C the adduct of 3 mois of ethylene oxide and of 4 mois of propylene oxide to a dodecyl
• the adducts of ethylene oxide and propylene oxide to higher molecular EXAMPLES might f 9 v yt the fatty aimhol 10
• the foam behavior of different cleansing and rinsing admixducis l shot ⁇ alkl'lene Wide fi are employed tures was examined for comparison purposes in a special foam due 1 biologicaldeci-lmpclsablmyexamination apparatus.
• the following table exhibits the ex- The individual components.
• the 8 rinsing tremely good foam behavior of the compositions of the invenagents of the invention-amount to approximately 70 l 5 tiom percent to 98 percent by weight of component A and 2 percent to 30 percent by weight of component B. in practice it was in particular that mixtures from 85 percent to 95 percent by weight of component A and 5 percent to percent by weight of component B are particularly suitable.
• concentrations of approximately 0.05 to 0.5 gnu/liter. preferably 0.1 to 0.4 gmJliter in the cleaning fluid are required.
• concentrations if employed as rinsing agent subsequent to an alkaline washing phase, approximately 0.01 to 0.25 gmJlltcr, preferably 0.02 to 0.1 gmJiiter are used. To a certain degree the concentrations are dependent upon the hardness of the water and the type of dishes. When washing or rinsing, utilizing hard and salty waters, or with plastic dishes, greater amounts of the rinsing agents are required.
• the compositions of the invention are prepared in the form of aqueous concentrates with a content of approximately l0 percent to percent by weight of mixtures of components A and B.
• the concentrates can be adjusted in such way that they possess a good temperature stability and do not tend to precipitate or separate into layers.
• the concentrates The foam apparatus as used was constructed in similu manner as a modern dishwasher operating according to the jet spray system. By means of a pump about 170 liters of water per minute were rotated and sprayed into the metering chamber by means of a rotating spray-arm provided with nozzles. Foam heads from 0 to 280 mm.
• the liquor temperature during the tests was C.
• the hardness of the water used was l6 dB
• the duration of the foam test lasted 5 minutes.
• the reading of the foam height was done immediately after the machine came to a standstill and 30 seconds after the machine had come to a stop.
• EXAMPLE IS A very low-foaming detergent for household dishwashers had the following composition:
• Low foaming rinsing and washing compositions adapted for dishwashers consisting essentially of (A) from 70 percent to 98 percent by weight of water-soluble polyvinyl alcohols obtained by hydrolysis of polyvinyl acetates, having a hydrolysis degree of between 85 percent and 90 percent and having a molecular weight of between 1,000 and 4,000, and (B) from 2 percent to 30 percent by weight of interface active compounds based on alkylene oxide adducts selected from the group consisting of l) a polyoxypropylene glycol having an average number of oxypropylene units of between 17 and 86, adducted with from 0 to 30 mol percent of oxyethylene units, the total number of oxypropylene and oxyethylene units in said adduct being l00 moi percent (2) a propylene oxide adduct of a hydrocarbon compound having from two to ID carbon atoms and at least two reactive hydrogen atoms selected from the group consisting of alk'anes, benzene and alkyibenz
• R-Y-H wherein R represents a radical having from eight to 36 carbon atoms selected from the group consisting of alkyl, alitenyl, al-
• kadienyl, monohydroxyalltenyl and allrylphenyl and Y represents a bridging link selected from the group consisting of O, S, COO, NH, CONH, and SO,Nl-l; adducted first with oxp'ethylenc units and thereafter with oxyalkylene units se ccted from the group consisting of oxypropylene and oxybutyiene, said oxyethylcne being from 0 to 70 moi percent of the total amount of oxyaiityiene units present; from two to 90 oxypropylene and oxybutylene units being present in said adduct.
• component B is a propylene oxide adduct of a hydrocarbon compound having from two to l0 carbon atoms and at least two reactive hydrogen atoms selected from the group consisting of alkanes, benzene and alkylbenzenes, substituted with substitutents selected from the group consisting of hydroxy, amino, and mixtures thereof, said propylene oxide adduct having an average number of oxypropylene units of between 27 and 68, adducted with from 0 to 30 moi percent of oxyethylene units, the total number of oxypropyiene and oxyethylene units in said adduct being lOO moi percent.
• R represents a radical having from eight to 36 carbon atoms selected from the group consisting of alkyl, alkenyl, alkadienyl, monohydroxyalkenyl and alkylphenyl and Y represents a bridging link selected from the group consisting of O, S, COO, NH, CONH, and SO NH: adducted first with oxyethylene units and thereafter with oxyalkyiene units selected from the group consisting of oxypropylene and oxybutylene, said oxyethylene being from 0 to 70 mol percent of the total amount of oxyalkylene units present; from 2 to 90 exypropyiene and oxybutylene units being present in said adduct.
• alkylene oxide adduct is the addition product of from 2 to 30 mois of propylene oxide to an alcohol having from eight to 22 carbon atoms selected from the group consisting of fatty alcohols and aikyiphenois.
• alkylene oxide adduct is the addition product of from 2 to 20 mois of ethylene oxide and from 2 to 30 mois of propylene oxide, to an alcohol having from eight to 22 carbon atoms selected from the group consisting of fatty alcohols and aikylphenols, wherein at least 30 mol percent of said alkyiene oxides is propylene oxide.
• Aqueous concentrates containing from 10 percent to 30 percent by weight of the low-foaming rinsing and washing compositions of claim 1.

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• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Detergent Compositions (AREA)

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Cited By (16)

Citations (3)

• 1968
  • 1968-03-14 DE DE19681692019 patent/DE1692019A1/de active Pending
  • 1968-11-29 FR FR1598231D patent/FR1598231A/fr not_active Expired
• 1969
  • 1969-02-17 US US799933A patent/US3635827A/en not_active Expired - Lifetime
  • 1969-03-10 CH CH355669A patent/CH524682A/de not_active IP Right Cessation
  • 1969-03-10 BE BE729638D patent/BE729638A/xx unknown
  • 1969-03-13 NL NL6903899A patent/NL6903899A/xx unknown
  • 1969-03-13 AT AT247569A patent/AT292155B/de not_active IP Right Cessation

Patent Citations (3)

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